Cladded amorphous metal products

ABSTRACT

An embodiment relates to a cladded composite comprising a cladding layer of a bulk metallic glass and a substrate; wherein the bulk metallic glass comprises approximately 0% crystallinity, approximately 0% porosity, less than 50 MPa thermal stress, approximately 0% distortion, approximately 0 inch heat affected zone, approximately 0% dilution, and a strength of about 2,000-3,500 MPa.

RELATED APPLICATION

The present application claims priority to U.S. Provisional ApplicationNo. 62/826,630, entitled “CLADDED AMORPHOUS METAL PRODUCTS” filed onMar. 29, 2019, which is incorporated herein by reference in itsentirety. The present application is related to the following USApplications which are incorporated herein by reference in theirentirety:

Attorney Docket Application Filing No. No. Title Date LQMC-010-16/575,842 ADDITIVE MANUFACTURING Sep. 00US OF IRON-BASED AMORPHOUS 19,METAL ALLOYS 2019 LQMC-012- 16/584,085 SENSOR AND RFID HOUSING Sep. 00USENCLOSURE FOR THIN WALL 26, COMPONENTS 2019 LQMC-013- 16/599,138 SYSTEMAND METHOD FOR Oct. 00US APPLYING AMORPHOUS METAL 11, COATINGS ONSURFACES FOR 2019 THE REDUCTION OF FRICTION LQMC-011- 16/731,609 SYSTEMAND METHOD FOR Dec. 00US APPLYING HIGH TEMPERATURE 31, CORROSIONRESISTANT 2019 AMORPHOUS BASED COATINGS LQMC-014- 16/731,292 STRUCTUREDAMORPHOUS Dec. 00US METALS (SAM) FEEDSTOCK 31, AND PRODUCTS THEREOF 2019

FIELD OF THE INVENTION

This invention relates to the process of preparing cladded surfaces forgenerating functional surfaces including wear, corrosion and erosionresistance functionalities. The invention is more particularly concernedwith a process involving amorphous material alloys and ultrasonicprocessing.

BACKGROUND OF INVENTION

Amorphous materials are often not considered in engineering applicationsdue to their low fracture toughness, difficulty in joining to othermaterials, and structure scale-up challenges. In addition, severalmethods, processes and materials have been used to manufactured claddedsurfaces including roll bonding, co-extrusion, weld overlay and lasercladding. They are not only labor and time intensively, but also mayhave difficulties to achieve the desired specifications.

In the past two or three years, a number of additive manufacturing (AM)technologies have shown the ability to produce amorphous metalstructures due to high cooling rates in melt pools or low processingtemperatures.

Processing of novel materials, manufacturing complex-shaped parts,reduction in part manufacturing, reduction in finishing time, andlowering the cost are the drivers for using AM. AM is particularlysuitable for the manufacture of products with complex features usingtraditionally difficult-to-process materials without the use oftraditional tools, such as molds or dies. AM, also referred to as 3Dprinting, is a cladding layer-by-layer technique of producingthree-dimensional (3D) objects directly from a digital model. AM hasbecome a very disruptive field in the manufacturing sector and continuesto grow in use.

This manufacturing disruption is allowing scale-up and creation ofcomplex amorphous structures outside of traditional casting methods.Consequently, amorphous alloy use is actively expanding into newapplication areas which were previously deemed impossible. However, theductility and fracture toughness of printed and cast amorphous alloysremains subpar of many crystalline metals, which continues to limit usein many engineering applications. By mixing amorphous alloys with othermetals with high ductility and fracture toughness, these limitations maybe overcome.

BMG laminate composites have been created in prior art, yet these areepoxy based structures. Epoxy is unfavorable for extreme temperatureconditions, which is where many BMGs are used. Additionally, these epoxyjoints do not hold-up to high cycling and loading due to poor bondstrength. One example of this poor bond strength is shown in a BMG balland cone locator (obtained from Aerospace Science and Technology, Vols.82-83, pp. 513-519, November 2018). The ball and cone locator are usedfor docking and moving things around in low earth orbits and space. Forlow earth orbits, low melting point materials are of interest such thatmaterials burn-up or disperse during re-entry to earth. This greatlyminimizes the risk of solid's entering and potentially causing damage,i.e., steels and titanium alloys. Consequently, BMGs are of interest toreplace titanium ball and cone locators due to their high hardness andlow melting point. However, the bond strength with epoxy is notadequate. A solution to this bond problem would be to replace the bodyof the cone with aluminum and use BMGs only on the cone face.

Currently cladding of surfaces with BMGs currently does not use metallicjoining as the mechanism. Instead, mechanical interlocking is used bydepositing BMG droplets via cold spray onto a mechanically roughenedsurface. This mechanical interlocking has limitations in its operatingtemperature and strength, similar to epoxy. By replacing this bond witha metallurgical one, operating temperature and strength becomes less ofa concern.

Out of the available additive technologies for BMG production,Ultrasonic Additive Manufacture (UAM) has the lowest processingtemperature, which in turn allows the creation of dissimilar ormulti-metal structures since solidification is absent and hightemperature chemistry and diffusion are suppressed. UAM is frequentlyused to create dissimilar metal laminate composites or clad metalsurfaces due to these attributes. Dissimilar metal composites createdusing UAM are frequently composed of a soft ductile material and aharder brittle material to create tailorable mechanical response andfailure behavior. Similarly, cladding of surfaces often begins byjoining hard, wear-resistant metals to softer underlying structure.Cladding of hard metals to hard metals has also been achieved but isless commonly encountered.

Amorphous metals are a new class of materials that have a disordered,non-crystalline, glassy structure, lacking long-range periodicity of theatomic arrangement, that are created when metals or their alloys areeither cooled very quickly or because of a unique alloy combination,bypassing crystallization during solidification. FIG. 1 shows thetime-temperature-transformation (TTT) solidifying diagram of anexemplary amorphous and a crystalline alloy. The C shape of crystallinematerials in TTT diagram is the result of the competition between theincreasing driving force for crystallization and the slowing of kinetics(effective diffusivity) of the atoms. Both thermodynamic and kineticparameters affect the crystallization and shift the C shape position tolarger times.

The position of the nose determines the critical cooling rate to avoidnucleation and crustal growth during cooling and defines the conditionsto manufacture amorphous alloys. In case of amorphous alloys instead ofliquid/solid crystallization transformation, the molten material becomesmore viscous as the temperature reduces near to the glass transformationtemperature and transforms to a solid state after this temperature. Inthe liquid state, the atoms vibrate around positions and have nolong-range ordering. Hence, the critical cooling rate is determined byatomic fluctuations, controlled by thermodynamic factor, rather thankinetic factor. Due to the crystallization bypass, the amorphous alloysremain the most prominent characteristics of the liquids, the absence oftypical long-range ordered pattern of the atomic structure ofcrystalline alloys and any defects associated with it. This disordered,dense atomic arrangement determines the unique structural and functionalproperties of amorphous alloys.

Due to their unique microstructure, amorphous metals combine highcorrosion resistance, high strength, high hardness and substantialductility in one single metal. The unique properties or amorphous metalscomes from the lack of long-range periodicity, related grain boundariesand crystal defects such as dislocations. There has been a limitationregarding manufacturing net-shape components with Amorphous Metals untilonly recently with the additive manufacturing. Traditionally, componentswere limited in thickness to 3-5 mm due to the fast cooling raterequirement of the alloy (critical casting thickness).

Amorphous materials are often not considered in engineering applicationsdue to their low fracture toughness, difficulty in joining to othermaterials, and structure scale-up challenges. In addition, severalmethods, processes and materials have been used to manufactured claddedsurfaces including roll bonding, co-extrusion, weld overlay and lasercladding. They are not only labor and time intensively, but also mayhave difficulties to achieve the desired specifications.

Additive manufacturing has remedied some of these challenges by enablingmore complex features and larger structures above the critical castingthickness. Yet, printed structures demonstrate lower ductility andfracture toughness due to micro defects from printing. This decrease infracture toughness creates pause for design engineers, which ultimatelyinfluences BMG use. Applicant believes this decrease in fracturetoughness and ductility can be overcome by mixing cast BMG foils withmore ductile alloys, i.e., form a metallic composite.

The UAM process works by building up solid metal objects throughultrasonically welding a succession of metal tapes or foils into a 3Dshape, with periodic machining operations to create the detailedfeatures of the resultant object. The process creates a joint betweenthe foils through plastic deformation and not heat. The bond zone istypically near 10 microns in size and composed of equiaxedrecrystallized grains when joining similar metals. For dissimilar metaljoints, the bond zone is sub-micron in size and does not always containnew crystals. Due to the small bond zone relative to the foil stocksize, bulk material property changes are negligible and identical to theincoming foil stock.

CN106862748A demonstrates amorphous/metal micro-laminated compositematerial ultrasonic wave accumulation manufacture method, which includesextracting the individual-layer data, amorphous/metal foil issuccessively welded using ultrasonic consolidation technology in metalfoil substrate to obtain amorphous/crystalline metal micro-laminatedcomposite.

U.S.20190232430 A1 discloses additive manufacturing of amorphous alloyusing laser 3D printing of an amorphous alloy foil using the amorphousalloy foil as a raw material. However, laser 3D printing is based onmelting of amorphous foils to generate the bonding between the foils.

WO2018/089080 A1 describes an additive manufacturing system which uses amaterial joining laser system to join together foil sheets to form ametal part. The material joining laser system can be configured to joinadjacent foil sheets together in a substantially uniform manner. Acooling system is required in this case to maintain the amorphousstructure of the foils. In other cases, an amorphous based/crystallinecomposite will be generated.

KR100549997B1 discloses a method for manufacturing amorphous compositematerial consisting of an amorphous surface, and the surface of theamorphous base metal having a sufficient ductility and fracturetoughness at low production cost. The amorphous surface of the compositematerial has good corrosion resistance, wear resistance, hardness andstrength and the like useful in various industries. Since the processingis done at melting point through the electron beam, amorphous feedstocktransforms to crystalline (either partially or fully) and generatecomposites with different amorphous portion.

U.S.20180339338A1 describes method to use 3D printing of discrete thinlayers during the assembly of bulk parts from metallic glass alloys withcompositions selected to improve toughness at the expense of glassforming ability.

CN107498173 A discloses a laser-assisting type ultrasonic additivemanufacturing device for a metallic foil tape and a manufacturing methodwhich combines ultrasonic welding with laser processing.

In the embodiments herein, metallurgical bonding of the amorphous foilto the substrate is performed using ultrasonic additive manufacturing.The process creates a joint between the foils through plasticdeformation. Since the processing is done at near room temperature,there are no transformation issues after build-up such in case ofelectron beam and no cooling is required to keep the amorphousstructure.

SUMMARY OF INVENTION

An embodiment relates to a cladded surface such as metallic surface orthe like using amorphous metallic alloys.

An embodiment includes method for manufacturing of amorphous metal alloylaminate composites and cladding of metallic surfaces by usingultrasonic additive manufacturing (UAM).

An embodiment includes a method for metallurgically bonding claddingmaterial onto a metal substrate.

Such embodiment further includes the metallurgical bonding of theamorphous foil to the substrate using UAM.

In an embodiment, UAM process creates a joint between the foils throughplastic deformation. The bond zone formed by joining similar metals isabout 10 microns in size and composed of equiaxed recrystallized grains.The bond zone formed by joining dissimilar metal joints is aboutsub-micron (less than a micron) in size and does not always contain newcrystals. Due to the small bond zone relative to the foil stock size,bulk material property changes are negligible and identical to theincoming foil stock.

An embodiment relates to creation of ductile and fracture resistant BMGstructures via composite theory.

An embodiment relates to a cladded composite comprising at least acladding layer of a bulk metallic glass and a substrate; wherein thebulk metallic glass comprises approximately 0-10% crystallinity,approximately 0% porosity, less than 50 MPa thermal stress,approximately 0% distortion, approximately 0 inch heat affected zone,approximately 0% dilution, and a strength of about 2,000-3,500 MPa.

In other embodiments, the bulk metallic glass comprises Zr, Cu; whereinthe substrate comprises steel.

The bulk metallic glass further comprises Ni, Al.

The cladding layer has a thickness of about 0.02 mm to 5 mm.

The cladding layer comprises multiple sheets of the foil.

The bulk metallic glass comprises Zr, Cu, Ni, Al; wherein the substratecomprises aluminum.

The cladding layer comprises a foil having a foil thickness of about20-200 μm; wherein the cladding layer has a thickness of about 0.02 mmto 5 mm.

The cladding layer comprises a foil having a foil thickness of about20-300 μm; wherein the cladding layer has a thickness of about 0.02 mmto 5 mm.

The cladding layer comprises a foil having a foil thickness of about20-300 μm; wherein the cladding layer has a thickness of about 0.02 mmto 5 mm.

The cladded composite comprises a bond layer comprising Ni.

The bulk metallic glass comprises Zr, Cu; wherein the substrate istitanium.

The cladding layer comprises a foil having a foil thickness of about20-300 μm; wherein the cladding layer has a thickness of about 0.02 mmto 5 mm.

The bulk metallic glass further comprises Ni, Al; wherein the claddinglayer comprises a foil having a foil thickness of about 20-300 μm;wherein the cladding layer has a thickness of about 0.02 mm to 5 mm.

The bulk metallic glass further comprises Ti, wherein the cladding layercomprises a foil having a foil thickness of about 20-300 μm; wherein thecladding layer has a thickness of about 0.02 mm to 5 mm.

The bulk metallic glass comprises Ni, Si; wherein the substrate issteel; wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm; wherein the cladding layer has a thicknessof about 0.02 mm to 5 mm.

The bulk metallic glass comprises Co, Fe; wherein the substrate issteel; wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm; wherein the cladding layer has a thicknessof about 0.02 mm to 5 mm.

The bulk metallic glass comprises Ti, Zr; wherein the substrate isaluminum; wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm; wherein the cladding layer has a thicknessof about 0.02 mm to 5 mm.

The cladded composite further comprises an interlayer, wherein theinterlayer and the substrate have a disjoint crystal of less than <1micron in size.

The bulk metallic glass comprises no crystallinity, no porosity, nothermal stress, no distortion, no heat affected zone and no dilution.

The bulk metallic glass comprises a first bulk metallic glass and thesubstrate comprises a second bulk metallic glass.

An embodiment relates to an ultrasonic additive manufacturing process,comprising: joining a foil comprising a bulk metallic glass to asubstrate; and forming a cladded composite comprising the foil and thesubstrate; wherein a thickness of the cladded composite is greater thana critical casting thickness of the bulk metallic glass.

In other embodiments:

The thickness of the cladded composite is greater than the criticalcasting thickness of the bulk metallic glass by a factor of at least 15.

The ultrasonic additive manufacturing process comprises an amplitude inrange of 30 μm to 40 μm and a speed in range of 50 inch per minute to150 inch per minute.

The substrate comprises Al, Ti, steel.

There is no interlayer is between the bulk metallic glass and thesubstrate.

There is an interlayer is between the bulk metallic glass and thesubstrate.

The bulk metallic glass and the substrate has an interface; wherein theinterface is amorphous.

The bulk metallic glass and the substrate has an interface; wherein theinterface has no Kikuchi pattern.

The ultrasonic additive manufacturing process further comprises makingthe foil; modifying a surface of the foil; optionally removing a surfaceoxide layer of the foil; and forming a nascent contact of the foil withthe substrate.

DESCRIPTION OF FIGURES

FIG. 1 shows a schematic Time-Temperature-Transformation (TTT) diagramthat shows crystallization kinetics amorphous metals vs. crystallinemetals.

FIG. 2 shows UAM process: a) Additive stage; b) CNC subtractive stage.

FIG. 3 shows a) joined ZrCu-based BMGs with UAM and b) light microscopyof a joint cross-section

FIG. 4 shows mechanical properties of amorphous metals.

FIG. 5 shows an example of the XPS spectra pattern.

FIG. 6 shows measured oxide layer thicknesses on both sides of foils forUAM.

FIG. 7 shows cladding crystalline metals with amorphous alloys in UAMwithout using soft interlayers.

FIG. 8A shows Zr based BMG alloy foils were UAM processed onto Titaniumsubstrate using UAM with Al as interlayer.

FIG. 8B shows 6 layered Zr used for cladding.

FIG. 9 shows cladding of 4130 alloy steel substrate with Zr basedalloys. Ni 200 is used when joining the initial layer using UAM.

FIG. 10 shows EBSD results cladded 4130 alloy steel with 3 layers of Zrbased alloys using Ni 200 as initial joining near the sublayer and inthe bulk.

FIG. 11 shows Push-pin interface characterization. The test found that(i) the aluminum transition layer does not weaken the structure, and(ii) failure occurs through the deposit instead of along interfaces.

DETAILED DESCRIPTION Definitions and General Techniques

The following description is made for the purpose of illustrating thegeneral principles of the embodiments herein and is not meant to limitthe inventive concepts claimed herein. Further, particular featuredescribed herein can be used in combination with other describedfeatures in each of the various possible combinations and permutations.

It must also be noted that, as used in the specification and theappended claims, the singular forms “a,” “an” and “the” include pluralreferents unless otherwise specified. Any ranges cited herein areinclusive.

The terms “substantially” and “about” and “near” and “approximate” usedthroughout this specification are used to describe and account for smallfluctuations. For example, they can refer to less than or equal to ±5%,such as less than or equal to ±2%, such as less than or equal to ±1%,such as less than or equal to ±0.5%, such as less than or equal to±0.2%, such as less than or equal to ±0.1%, such as less than or equalto ±0.05%.

Bulk-solidifying amorphous alloys, or bulk metallic glasses (“BMG”), area recently developed class of metallic materials. These alloys may besolidified and cooled at relatively slow rates, and they retain theamorphous, non-crystalline (i.e., glassy) state at room temperature.Amorphous alloys have many superior properties, e.g., physicalproperties, then their crystalline counterparts. However, if the coolingrate is not sufficiently high, crystals may form inside the alloy duringcooling, so that the unique benefits of the amorphous state can be lost.For example, one challenge with the fabrication of bulk amorphous alloyparts is the partial crystallization of parts due to either slow coolingor impurities prevalent in the raw alloy material. As a high degree ofamorphicity (and, conversely, a low degree of crystallinity) isdesirable in BMG parts, there is a need to develop methods for castingBMG parts having predictable and controlled amount of amorphicity. Theterms “bulk metallic glass” (“BMG”), bulk amorphous alloy (“BAA”), andbulk solidifying amorphous alloy are used interchangeably herein.

Additive is something added to alter or improve the quality of an item.

The term “metal” or “metallic” refers to an electropositive chemicalelement.

Amorphous is defined as lacking in long-range order. It alsocharacterized by random atomic orientation. It excludes partiallycrystalline and metastable crystalline metal alloys.

An “amorphous alloy” is an alloy having an amorphous content of morethan 50% by volume, preferably more than 90% by volume of amorphouscontent, more preferably more than 95% by volume of amorphous content,and most preferably more than 99% to almost 100% by volume of amorphouscontent. Note that, as described above, an alloy high in amorphicity isequivalently low in degree of crystallinity. An “amorphous metal” is anamorphous metal material with a disordered atomic-scale structure. Incontrast to most metals, which are crystalline and therefore have ahighly ordered arrangement of atoms, amorphous alloys arenon-crystalline. Materials in which such a disordered structure isproduced directly from the liquid state during cooling are sometimesreferred to as “glasses.” Accordingly, amorphous metals are commonlyreferred to as “metallic glasses” or “glassy metals.” In one embodiment,a bulk metallic glass (“BMG”) can refer to an alloy, of which themicrostructure is at least partially amorphous. However, there areseveral ways besides extremely rapid cooling to produce amorphousmetals, including physical vapor deposition, solid-state reaction, ionirradiation, melt spinning, and mechanical alloying. Amorphous alloyscan be a single class of materials, regardless of how they are prepared.Bulk-solidifying amorphous alloys, or bulk metallic glasses (“BMG”) maybe solidified and cooled at relatively slow rates, and they retain theamorphous, non-crystalline (i.e., glassy) state at room temperature.Amorphous alloys have many superior properties than their crystallinecounterparts. However, if the cooling rate is not sufficiently high,crystals may form inside the alloy during cooling, so that the benefitsof the amorphous state can be lost. For example, one challenge with thefabrication of bulk amorphous alloy parts is partial crystallization ofthe parts due to either slow cooling or impurities in the raw alloymaterial. As a high degree of amorphicity (and, conversely, a low degreeof crystallinity) is desirable in BMG parts, there is a need to developmethods for casting BMG parts having controlled amount of amorphicity.

Cladding is defined as a process to enrich the surface properties of thematerial. The properties such as hardness, wear, and corrosionresistance are of major concerns in the various mechanical andtribological applications. During the cladding process, the surface ismodified by the addition of a new layer with the desired powdermaterials.

The critical casting thickness is the maximum thickness that a BMG canbe cast. This thickness is different for each BMG alloy composition. Inembodiments herein, the BMG alloy has a thickness larger than itscritical casting thickness.

Distortion means the change in shape.

Porosity or void fraction is a measure of the void (i.e. “empty”) spacesin a material, and is a fraction of the volume of voids over the totalvolume, between 0 and 1, or as a percentage between 0% and 100%.

Heat affected zone is the region affected by change in temperature to amaterial.

Thermal Stress is stress created by any change in temperature to amaterial. These stresses can lead to fracture or plastic deformationdepending on the other variables of heating, which include materialtypes and constraints.

Dilution is the proportion of a base material from the substate in thecladding layer material,

Foil is defined as thin sheet of a material.

Interlayer is defined as the cladding layer situated between two layers.

Joint is defined as a place where two things or parts are joined orunited; an area at which two ends, surfaces, or edges are attached.

Disjoint crystals are defined as crystals that are dislocated fromeach-other and do not have any contact point to each other Bond layer isa cladding layer of material designed to adhere another layer to asubstrate.

Void is a pore that remains unfilled with polymer and fibers in amaterial. Voids are typically the result of poor manufacturing of thematerial and are generally deemed undesirable. Voids can affect themechanical properties and lifespan of the composite. It is gaps orspaces which extend in the space between the top and bottom ends It isalso defined as empty space, opening, gap, the quality of being withoutsomething.

Plastic is a material which, when subjected to compression at ambienttemperatures, will flow before it will crack or break.

Interface is a surface regarded as the common boundary of two bodies,spaces, or phases. It is a general term to describe the connecting linkbetween the two systems

Transition is a passage from one state, condition, or place to another.

Lattice is a regular geometrical arrangement of points or objects overan area or in space.

Pulsed in a simple term is a load that requires intermittent pulses ofpower rather than a constant level of power.

Crystalline material is defined as a solid material whose constituents(such as atoms, molecules, or ions) are arranged in a highly orderedmicroscopic structure, forming a crystal lattice that extends in alldirections. Crystals are also defined as crystalline material.

Composites is defined as a composite material (also called a compositionmaterial or shortened to composite, which is the common name) is amaterial made from two or more constituent materials with similar ordifferent physical or chemical properties that, when combined, produce amaterial with characteristics different from the individual components.The individual components remain separate and distinct within thefinished structure, differentiating composites from mixtures and solidsolutions. Composite is made up of several parts or elements or, withrespect to constructional material, made up of recognizableconstituents.

Laminate is a material formed by bonding two or more materials togetheras in a pressure sensitive construction. Laminate and Composite may beused interchangeably throughput the specification.

An embodiment addresses the limitations of prior art that disclose highcorrosion resistance, high toughness and high erosion resistance. Theembodiments herein relate to a new class of materials said amorphousmetals that offer high corrosion protection both under low and hightemperatures. Further, the said material is designed in such a way thatit does not increase the weight of the assembly.

In an embodiment, the cladded composite comprises a substrate and atleast a cladding layer comprising a foil comprising a bulk metallicglass on the substrate; wherein the bulk metallic glass comprisesapproximately 0-10% crystallinity, approximately 0% porosity, less than50 MPa thermal stress, approximately 0% distortion, approximately 0 inchheat affected zone, approximately 0% dilution, and a strength of about2,000-3,500 MPa.

The bulk metallic glass comprises alloys based on Zr, Cu, Ni, Al, Ti,Hf, Si, B, C, P, Co, Fe, Mo, or combinations thereof.

The bulk metallic glass comprises alloys based on ZrCu, NiAl, ZrTi,NiCu, NiCuHf, NiAlTi, NiSi, BC, NiP, PC, CoFe, NiMo, BSi, orcombinations thereof.

The substrate comprises steel, aluminum, titanium or combinationthereof.

The foil has a foil thickness in a range of 5-1000 μm, 10-750 μm, 20-500μm, 30-300 μm, 40-200 μm, 50-100 μm, or any combinations thereof.

The number of foils in the cladding layer could be 1-100, 2-75, 3-50,4-40, 5-25, 6-60, 7-10 or any combinations thereof.

The cladding layer has a thickness in a range of about 0.02-5 mm,0.1-2.5 mm, 0.15-1.5 mm, 0.2-1 mm, 0.25-0.8 mm, 0.3-0.7, 0.35-0.6 mm,0.4-0.55 mm, 0.45-0.5 mm or any combinations thereof.

In an embodiment, UAM process to generate BMG composite and claddedstructures while maintaining the amorphous microstructure.

In an embodiment, UAM process works by building up solid metal objectsthrough ultrasonically welding a succession of metal tapes or foils orlike into a 3D shape, with periodic machining operations to create thedetailed features of the resultant object. The process creates a jointbetween the foils through plastic deformation and not heat.

In an embodiment, UAM creates a bond zone. In one embodiment, forsimilar metals joints, bond zone is composed of equiaxed recrystallizedgrains. The bond zone is around microns, preferably near 5 microns ornear 10 microns or 20 microns in size. In another embodiment, fordissimilar metal joints, the bond zone is sub-micron in size. Thedissimilar metal contains a new crystal. In another embodiment,dissimilar metal joint does not contain new crystals. Due to the smallbond zone relative to the foil stock size, bulk material propertychanges are negligible and identical to the incoming foil stock.

In an embodiment, UAM process has both additive and subtractive steps inarriving at a final part shape. In another embodiment, UAM has onlyadditive step in arriving at a final part. In another embodiment, UAMhas only subtractive step in arriving at a final part shape.

In an embodiment, the additive and subtractive stage of the UAM processis shown in FIG. 2. FIG. 2a shows the additive stage of the UAM process,consisting of two ultrasonic transducers and a (welding) sonotrode. Thevibrations of the transducer are transmitted to the disk-shaped weldingsonotrode, which in turn creates an ultrasonic solid-state weld betweenthe thin metal tape/foil or like and base plate. The continuous rollingof the sonotrode over the plate welds the entire tape/foil or like tothe plate. During the build, periodic machining operations add featuresto the part. FIG. 2b shows subtractive stage to remove excess tape/foilor like material and true-up the top surface for the next stage ofwelds. Thus, the additive manufacture (AM) process involves bothadditive and subtractive steps in arriving at a final part shape. Thistechnology is patented by Fabrisonic.

In an embodiment, UAM is used to create dissimilar metal laminatecomposites or clad metal surfaces. In an embodiment, dissimilar metalcomposites created using UAM are composed of a soft ductile material anda harder brittle material to create tailorable mechanical response. Inan embodiment, cladding of surfaces begins by joining hard,wear-resistant metals to softer underlying structure.

In an embodiment, UAM is used to clad of hard metals to hard metals.

In an embodiment, UAM metallically join BMG foils to other BMG foilswith suppressed crystallinity formation. In other embodiment, UAM createdissimilar BMG laminate metal composites and clad metal surfaces withBMGs using metallic joints. In an embodiment, interface of BMG isremedied by cladding aluminum with BMGs.

In an embodiment UAM is used for processing of novel materials andmanufacturing complex-shaped parts. In an embodiment, UAM reduces inpart manufacturing. UAM is particularly suitable for the manufacture ofproducts with complex features using traditionally difficult-to-processmaterials without the use of traditional tools, such as molds or dies.

In an UAM is also referred to as 3D printing. UAM is a claddinglayer-by-layer technique of producing three-dimensional (3D) objectsdirectly from a digital model.

In an embodiment, UAM is creates more ductile and fracture resistant BMGstructures. In an embodiment ductile and fracture resistant BMGstructures is formed via composite theory.

In an embodiment, enhanced ductility and fracture toughness will comefrom other metals used in the laminate or base metal as cladding. In anembodiment, UAM join BMG foils to alternative metals. The no hightemperature chemistry in UAM allows multi-material joining. In anembodiment, UAM clad surfaces and fabricate dissimilar metal laminatecomposites without formation of new phase.

In an embodiment, UAM clad surfaces and fabricate dissimilar metallaminate composites. In an embodiment, UAM clad surfaces and fabricatedissimilar metal laminate composites without formation of new phase.

In an embodiment, UAM clad surfaces and fabricate dissimilar metallaminate composites, e.g., titanium and aluminum. There is no shift intransformation temperatures or change in heat transfer, which implieslittle to no formation of new phases.

In an embodiment, UAM provides a method to ease fabrication. BMG castingis tricky and requires special fixtures for fabrication and post processmachining that are time expensive and costly to make. UAM allows to bebuilt without the complicated fixtures and in-place machining operationsto expedite and simply finishing. i.e., no additional fixtures orreferencing.

In an embodiment a method to decrease in fracture toughness andductility of BMG is provided. In an embodiment a method to form a moreductile metal composite comprise mixing cast BMG foils with more ductilealloys is provided.

In an embodiment, UAM process avoid material damage.

In an embodiment, UAM produced metal composites has a solid-statenature.

In an embodiment, BMG alloys is manufactured in thin foil form. In anembodiment, BMG alloys is manufactured in thin foil form for claddingapplications.

In an embodiment, the surface of BMG alloy is modified. In anembodiment, the surface of BMG foil is modified. In an embodiment, thesurface of rolled BMG foil is modified. In one embodiment, themodification of the surface is to remove oxygen content. In anotherembodiment, the modification of the surface is to flatten the foil. Thefoils with thicker oxide scales and flatness variation have beenchallenging to weld. In one embodiment, the surface of BMG foils can bemodified using commercially available cleaning technologies to enablejoining for certain BMG alloys. Thick oxide layers restrict bonding incertain cases. The surface modification removes thick oxide layers whichlimits bonding in some cases.

In an embodiment, surface modification is done by various techniques butnot limited to laser system, energy beams, periodic reverseelectrocleaning (PRC) or any similar. In an embodiment, surfacemodification is done by a Laser system. The laser system is similar toP-Laser system. The laser system that uses laser energy to remove theoxide layers from the metal substrates. The oxide layer absorbs thelaser energy very well, while the pure metal or BMG reflects most of theenergy. The laser used will be pulsed on the surface with a frequency ofabout 200,000 pulse/s.

In an embodiment, surface modification is done using energy beams. Theenergy beams are Plasma or E-beam energy sources, that use either plasmaor E-beam source to sputter the oxide layers and leave an oxide freefoils ready to be solid-state welded

In an embodiment, surface modification is done using periodic reverseelectrocleaning (PRC). PRC removes oxides and scales from metallicalloys. The etching is made alternately cathodic and anodic using DCcurrent.

In an embodiment, UAM process comprises breaking of the surface oxidelayers through scrubbing at the surfaces. The scrubbing is between theweld foils and tooling. The scrubbing forms nascent metal-to-metalsurface contacts, which creates a solid-state bond between the foils.

In an embodiment, UAM creates a solid-state bond between the foils afterthe oxide scale is broken through via the scrubbing action between thetop foil and bottom foil surfaces. In an embodiment, oxide scalecharacterization of foil is performed using but not limited to ahigh-performance multi-technique surface science instrument combininghigh-sensitivity X-ray photoelectron spectroscopy (XPS) with a dualanode Al/Ag monochromatic X-ray source, high resolution scanning fieldemission Auger electron spectroscopy and microscopy (AES, SAM),ultraviolet photoelectron spectroscopy (UPS), ion scatteringspectroscopy (ISS) and reflection electron energy loss spectroscopy(REELS). The FIG. 5 shows an example of the spectra pattern to analyzeoxygen scale thickness.

In an embodiment, the oxide scale thickness is determined using thefollowing equation:

${t_{oxide} = {{\lambda_{oxide} \cdot \sin}\; {\theta \cdot \ln}\left\lfloor {\left( {\frac{I_{base}^{\infty}}{I_{oxide}^{\infty}}\frac{I_{oxide}^{{ex}\; p}}{I_{base}^{e\; {xp}}}} \right) + 1} \right\rfloor}},$

where λ_(oxide) is the attenuation length, θ is the angle between thesample surface plane and the electron analyzer and the Is are themeasured peak intensities.

In an embodiment, UAM process comprises various BMG alloys. In anembodiment, UAM process comprises various BMG alloys and amorphousmaterials. In an embodiment, UAM process comprises various BMG alloysand crystalline materials. In an embodiment, the UAM process uses butnot limited to ZrCu based BMG alloys, aluminum alloys, and titaniumalloys. The FIG. 3 shows joining ZrCu-based BMGs with UAM.

In an embodiment, UAM process comprise various parameters. Theseparameters include but not limited to linear travel speed, tool pressureor down force, and oscillation amplitude and etc.

In an embodiment, the UAM process is used for scale-up. In anembodiment, various combination of composite and cladding for scale-upis selected using a go/no go screening approach. The process ofultrasonic welding of amorphous thin foils can be conducted according toinformation and data from the US Patent U.S. 20140312098; which isincorporated herein in entirety.

In an embodiment, UAM creates weld joint between the BMG alloy andcrystalline metal. In an embodiment, the weld joint is similar, betweenthe BMG alloy and crystalline metal. In an embodiment, the weld joint isdissimilar, between the BMG alloy and crystalline metal.

In an embodiment, the crystallinity between BMG alloy foils isquantified. The quantification of crystallinity between BMG alloy foilsis done by techniques such as but not limited to x-ray diffraction(XRD), electron backscatter diffraction (EBSD), energy dispersionspectroscopy (EDS), tunneling electron microscopy (TEM), ScanningElectron Microscopy (SEM) or any similar. The quantification ofcrystallinity between BMG alloy foils is done by techniques but notlimited to EDS, EBSD, if crystallinity is expected from the dissimilarmetal joint.

In an embodiment, UAM is used for several BMG alloys cladded to variouscrystalline substrates. In an embodiment, multiple BMG alloys is claddedto various crystalline substrates has little to no crystallinity orintermetallic phase formation. The TEM near the interface region of aBMG foil interface found limited and disjoint nanocrystals less than <1micron in size. Prior cladding work with laser is composed largely ofcrystal structures, which limits integrity and system robustness longterm.

In an embodiment, compatibility of BMG with UAM is evaluated. In anembodiment, compatibility of BMG with UAM is evaluated usingconsolidation qualities between foils. The consolidation quality betweenfoils is but not limited to void density.

In an embodiment, compatibility of BMG with UAM is studied using but notlimited to high power microscopes, optical microscopic characterizationor similar. Little to no voids and the absence of crystal latticepatterns implies a well consolidated amorphous joint.

In an embodiment, mechanical testing is performed on multi-layercomponents to measure but not limited to interlaminar bond strength andtensile properties. In an embodiment, mechanical testing evaluatesmechanical properties scale with part size. In an embodiment, mechanicaltesting is used to compare within UAM BMG parts, compare between UAM BMGto BMG foil stock or combination thereof.

In an embodiment, mechanical testing parameters included but not limitedto tensile testing, shear, fatigue, and interlaminar bond strength.

In an embodiment, the interlaminar bond strength or out-of-planestrength is investigated by not limited to push-pin testing. Push-pintesting is a comparative test to help steer 3D printing parameterdevelopment for new metal combinations and alloys. The test is alsouseful for evaluating interlaminar bond strength without building a tallbuild. The test works by pushing on 3D printed material with a pin fedthrough a bind hole in the baseplate. This pin is then loaded and pushedthrough the sample until failure occurs. The build failure is insightfulto the interlaminar bond strength. The data curves from the push pintest can be used to benchmark against other weld metals and to gaugestrength

In an embodiment, the amorphous metal coatings and bulk materials hashigh strength, high toughness. In an embodiment, the amorphous metalcoatings and bulk materials has superior wear and corrosion resistancewith material costs two to five times lower than Ti- and Ni-basedalloys. In an embodiment, amorphous metals are better than conventionalmetals in every aspect as shown in FIG. 4.

In an embodiment relates to joining of various BMG alloys. In anembodiment relates to joined different BMG alloys and that joints wereamorphous

In an embodiment, UAM specimens exceed the critical casting thickness ofthe material by a factor of 15 or more in all dimensions. Despitedecreasing quench effect with increasing build thickness, x-raydiffraction analysis suggests that a fully amorphous structure wasmaintained throughout the build. In an embodiment, a low concentrationof sparsely distributed nano-grain clusters could be present. Techniquessuch as but not limited to high-resolution electron backscatterdiffraction scan can be used to evaluate the clusters.

The embodiments relate to novel applications of metallic glassesachievable through appropriate material design and optimization ofexisting additive manufacturing processes.

An embodiment relates to elimination of microcracking that is presentdue to a build-up of stresses during rapid solidification.

In an embodiment, cladding custom engineering solution is provided. Anembodiment works with new metallic combinations to create new materialswith properties not available through monolithic metals.

In an embodiment, UAM is used to clad exotic materials such as but notlimited to tantalum, europium, tungsten as well as mainstream alloyssuch as but not limited to aluminum copper and steel or combinationthereof.

In an embodiment, the UAM metals composite comprising amorphous metalcomponents can redefine the design paradigm of materials and components.The metal composites of UAM is 2 to 10 times better performance inseveral applications of the Defense and Aerospace industries. In anembodiment, UAM metals composite comprising amorphous metal componentscan be used for aerospace structure parts. UAM metal composites wouldenable pursuing applications which were beyond the reach of traditionalmaterials.

In an embodiment, UAM poses ability to have tighter production controlover mission-critical components. In an embodiment, UAM poses ability toprint components for legacy aircrafts/vehicles or similar.

In an embodiment UAM additive manufacturing of Amorphous Metals wouldturn a new page in U. S based manufacturing by enabling UAM metalcomposite to last longer, helping reduce CO₂ emissions caused duringmanufacturing of metal and composites, enabling production of preciseand multifunctional, unique components directly and indirectly leadingto reduced energy consumption and massive economic savings.

The embodiments herein have application in aerospace companies. AM morepreferably UAM avoids the up-front costs, long lead times, and designconstraints of conventional high-volume manufacturing techniques likeinjection molding, casting, and stamping. Aerospace companies often needparts with complex geometries to meet tricky airflow and coolingrequirements in jammed compartments. The nanostructured materials withlow density and unique properties that make the parts both hard andtough coupled with excellent corrosion- and wear-resistance would enablethese materials to be the ideal choice for AM in multiple applications.

Metal 3D printing has been widely adopted by several high valueindustries, e.g., aerospace and medical. Many of these industries alsoutilize BMGs in niche applications to leverage BMG properties, e.g.,coatings, thin high deformation components, etc. These industries havebeen resilient to combine metal Amorphous and BMGs due to the printedstructure not being amorphous and having defects. The embodiments hereinallow combination of BMG and amorphous metals, which could be used invarious application but not limited, as shown in Table 1.

TABLE 1 Applications of the embodiments in various fields. Fans andcompressor section of Several applications requiring high turbineengines strength and superior corrosion Other engine components (blades,resistance in energy, desalinization, disc, hubs, inlet guide vanes andpower, paper, automotive. cases) Sporting Goods (Gears for bikes, golfHypersonic vehicles (scramjet inlet clubs), Electronic and watch casingflap) Bearings Impellers Fuel nozzles Gears Struts Springs Hydraulicssystems

The embodiments herein can be used to provide amorphous alloys withenhanced properties and functionality similar to Grade 4/5 Titanium. Theembodiments relate to 3D Printed BMG alloys.

The embodiments are illustrated by the following working examples inwhich all parts and amounts are by weight unless otherwise stated. Thefollowing examples as described are not intended to be construed aslimiting the scope of the embodiments.

WORKING EXAMPLES Example 1: BMG Alloys Used in Embodiments Herein

The BMG alloys used in embodiments herein are shown in the Table 2. Thethickness of the foils varied between.

TABLE 2 BMG alloys used in UAM with their composition and number oflayers. Sample BMG Alloy BMG Alloy Composition 1 ZrCuNiAlZr(75.72%)Cu(14.2%)Ni(2.5%)Al(2.58%) 2 ZrTiNiCuHfZr(64.5%)Ti(14.7%)Ni(12.6%)Cu(7%)Hf(1.2%) 3 ZrTiNiHfZr(61.7%)Ti(17.3%)Ni(20%)Hf(1%) 4 ZrCu Zr(50%)Cu(50%) 5 ZrCuNiAlTiZr(65.7%)Cu(15.5%)Ni(11.7%)Al(3.7%) Ti(3.3%) 6 NiSiBCNi(91.74%)Si(4.5%)B(3.7%)C(0.06%) 7 NiPC Ni(91.74%)P(11%)C(0.1%) 8CoFeNiMoBSi Co(69%)Fe(4%)Ni(1%)Mo(2%)B(12%)Si(12%) 9 TiZrCuNiTi(40%)Zr(20%)Cu(20%)Ni(20%) 10 TiCrCuNi Ti(40%)Cr(20%)Cu(20%)Ni(20%) 11NiCrFeSiBPMo Ni(42.5%)Cr(16%)Fe(32%)Si(1.5%)B(0.5%) P(6%)Mo(1.5%)

Three different materials have been tested as substrates to evaluatecladding potential. These alloys were selected due to their common usein aerospace applications: Steel, e.g., 4140 steel; titanium, e.g., Tigrade 3; and aluminum, e.g., Al 6061.

The development began with feedstock characterization and UAM processoptimization. The FIG. 6 shows that one side of the foils has higheroxygen content than the other one. The foils were manufactured usingmelt spinning process. During this process, the molten alloy is squeezedthrough the nozzle using pressure onto the surface of a rapidly rotatingcopper wheel. The melt solidifies instantly. The side that is in contactwith the air looks shiny and is expected to have a thicker oxide scalethan the side in contact with the copper wheel.

Example 2: Cladding Crystalline Metals with Amorphous Alloys in UAMWithout Using Soft Interlayers

The Ti based amorphous alloys was cladded with Aluminum. The result isshown in FIG. 7. The result shows that bond is strong.

Example 3: Cladding Crystalline Metals with Amorphous Alloys in UAMUsing Soft Interlayers

The other substrates including Titanium and steel, BMG bond strength wasweak and alloys cracked. To remedy this transition joint challenge, anintermediary alloy layer is used. For aluminum and Ti, 0.001″ thick Al1100 is used. UAM processing parameters were 6000N down force, 50 in/mintravel speed, and 36 microns scrubbing amplitude. Joints betweencrystalline metals and amorphous alloys using Al 1100 are shown in FIG.9.

Example 4: Zr Based BMG Alloy Foils Were UAM Processed onto TitaniumSubstrate

Six separate layers were joined onto the Titanium substrate to reach atotal thickness of about 1 mm. The result is shown in FIG. 8 Theinterfaces between foils cannot be seen other than the joint betweenlayer 5 and 6. No defects, porosity or voids have been detected alongthe cladding. Very good adhesion and cohesion have been observed.Multiple BMG foils can be added to a structure to create a tailorablethickness. It is possible to create a structure larger than the criticalcasting thickness. Ti and Steel baseplates had similar processingparameters, Al required more scrubbing amplitudes due to stiffnessmismatch.

Example 5: The Processing Parameters For All Alloys

The processing parameters for all alloys evaluated is summarized in theTable 3. The processing parameters are consistent and reproducible.Processing differences originate in the mechanical properties of thecrystalline substrates, i.e., the more flexible the substrate, the moreweld amplitude is required. Qualitatively, the bonds between BMG alloyswere very similar between the different crystalline materials.

TABLE 3 The processing parameter of alloys cladded on the substratesusing UAM. Speed in Foil Total Cladding inch per Cladded Substrate No.of Thickness Thickness Amplitude Load minute Composite CompositionMaterial Layers [μm] [mm] [μm] [N] [ipm] 1Zr(75.72%)Cu(14.2%)Ni(2.5%)Al(2.58%) Steel 1-5 80 0.08-0.4  33-372,500-4,000 50-150 2 Zr(75.72%)Cu(14.2%)Ni(2.5%)Al(2.58%) Aluminum 1-3200 0.2-0.6 33-37 2,500-4,000 50-150 3Zr(75.72%)Cu(14.2%)Ni(2.5%)Al(2.58%) + Steel 1-4 200 0.2-0.8 33-372,500-4,000 50-150 Ni foil as bond layer 4Zr(75.72%)Cu(14.2%)Ni(2.5%)Al(2.58%) Steel 3 200 0.6 33-37 2,500-4,00050-150 5 Zr(75.72%)Cu(14.2%)Ni(2.5%)Al(2.58%) Titanium 6 200 1.2 33-372,500-4,000 50-150 6 Zr(64.5%)Ti(14.7%)Ni(12.6%)Cu(7%) Aluminum 1-3 600.06-0.18 33-37 2,500-4,000 50-150 Hf(1.2%) 7Zr(64.5%)Ti(14.7%)Ni(12.6%)Cu(7%) Steel 1-3 60 0.06-0.18 33-372,500-4,000 50-150 Hf(1.2%) 8 Zr(61.7%)Ti(17.3%)Ni(20%)Hf(1%) Aluminum1-3 60 0.06-0.18 33-37 2,500-4,000 50-150 9Zr(61.7%)Ti(17.3%)Ni(20%)Hf(1%) Steel 1-3 60 0.06-0.18 33-37 2,500-4,00050-150 10 Zr (50%) Cu (50%) Steel 1-4 100 0.1-0.4 30-37 3,500-4,000100-150  11 Zr (50%) Cu (50%) Titanium 1-4 100 0.1-0.4 30-37 3,500-4,000100-150  12 Zr(65.7%)Cu(15.5%)Ni( 11.7%)Al(3.7%) Steel 1-5 90 0.09-0.4530-40 2,500-4,000 50-150 Ti(3.3%) 13 Ni(91.74%)Si(4.5%)B(3.7%)C(0.06%)Steel 1-5 35 0.035-0.175 30-40 2,500-4,000 50-150 14Ni(91.74%)P(11%)C(0.1%) Steel 1-5 35 0.035-0.175 30-40 2,500-4,00050-150 15 Co(69%)Fe(4%)Ni(1%)Mo(2%)B(12%) Steel 1-5 75 0.075-0.375 30-402,500-4,000 100-150  Si(12%) 16 Ti(40%)Zr(20%)Cu(20%)Ni(20%) Aluminum 1-10 70 0.07-0.7 30-40 2,500-4,000 50-150

Example 6: Characterization of the UAM Cladded Foils

In an embodiment, Interface between the foil layers and any defects wereanalyzed through the light microscopy to understand the influence of theprocess parameters into the additive manufacturing of these foils andevaluate the overall quality of the cladding layers as well as thedegree of the bonding and type of the defects. In addition, measurementsof the final stack heights were performed to determine the average thickness reduction of the foils after the UAM process. Furthermore,Sectioning of the samples was performed using water-cooled abrasive sawfollowing by mounting. The cut samples were clamped using sample clipsbefore mounting. Samples were ground, coarse polished and final polishedsequentially with 400, 600, and 800 grit SiC papers in water, followedby 1200 grit SiC paper in ethanol to minimize surface pitting. Sampleswere polished using 6 μm, 3 μm, and finally 1 μm diamond compositepolishing cloth with diamond compound extender as lubricant. FIG. 9displays the optical micrographs of UAM treated samples. It is showingthat all currently tested alloys are considered “feasible” for the UAMprocess. The one-layer cladding of amorphous alloys demonstrated strongconsolidation. In FIG. 9, Ni 200 is used when joining the initial layer.The 3 layers stack of amorphous alloys demonstrated strongconsolidation.

Example 7: EBSD Analysis

In an embodiment, EBSD analysis has been conducted on some of thesamples to see if there is any crystallization of the interface afterUAM processing, since its crystallized interfaces could be hard andreduced the likelihood of the build-up. To analyze the microstructuralchanges in the interface as well as in the foil bulk after UAMprocessing, Electron Backscatter Diffraction (EBSD) was used. EBSD givescrystallographic information including crystal structure and orientationfrom Kikuchi diffraction patterns. Sample of the cladded 4130 alloysteel with 3 layers of Zr based alloys using Ni 200 as initial joiningfoil was evaluated using EBSD. The sample was analyzed at differentareas in the bulk, interface and near the interface.

FIG. 10 shows the optical microscopy and EBSD of a jointed BMGinterface. In all cases, we could not identify any Kikuchi patterns asshown in FIG. 10. The EBSD test results near the interface or thesublayer was similar to the bulk, meaning that the material is fullyamorphous and no hard, brittle phases were generated. The FIG. 10 showsthat crystalline phases were present only on the areas where the foilsare not bonded to the substrate of the other foil. On those areas, theoxide layer of the foils is still not broken from UAM process to createthe “cold” welding with the underlying layer. No new phase formation inthe interface was observed.

Example 8: Mechanical Characterization

In an embodiment, interface strength was evaluated via push-pin testing.The testing found that the joints were strong relative to the bulkmaterial. To measure the interlaminar bond strength or out-of-planestrength, the push-pin samples were manufactured. The test works bypushing on UAM processed sample with a pin fed through a bind hole inthe baseplate. This pin is then loaded and pushed through the sampleuntil failure occurs. The build failure is insightful to theinterlaminar bond strength.

Using this test, base plates cladded with BMG with or without analuminum bond layer were tested as shown in FIG. 11. Curves marked “BMG”correspond to the samples without bonding layer, while samples marked“Al” correspond to the samples with bonding layer. Data curves from thetest showed that the bonding with or without bonding layer is similar.Two of the samples had defects created during drilling for the push-pintesting. As expected because of those defects, their bonding was lessthan the other samples (purple and red lines in the graph). The testfound that (i) the aluminum transition layer does not weaken thestructure, and (ii) failure occurs through the deposit instead of alonginterfaces.

Table 4 shows the differences in properties between parts cladded withUAM and other cladding processes.

TABLE 4 Differences in properties between parts cladded with UAM andother cladding processes. Heat Affected Surface Thermal Zone CorrosionWear Finish as Process Bonding Structure Porosity Stress (HAZ) DilutionStrength Performance Performance Processed Weld Metallurgical/ 100% VeryHigh High High (3-8% Medium Medium Medium Poor overlay StrongCrystalline low (substrate (more on the (steel (because (rough) (1-3%)stress over than surface, 560-670 of high 700 MPa, 0.03 fully MPa)dilution) cladding inch) mixed stress less in the than 500 interfaceMPa) 25-50% dilution) Thermal Mechanical/ Fully and Low Very Low No HAZNo Medium Medium High Medium- Spraying Poor partially (1-10%) dilution(because Good amorphous (0%) of the (100-500 (0-90% porosity)microinches crystallinity) as sprayed) Laser Metallurgical/ PartiallyVery Low (less Very Low Very Medium High High Good Cladding Strongamorphous Low than 200 (0.02-0.03 Low (steel (800-1,2000 (20-100% (1-2%)MPa) inch) (less 560-670 microinches) crystallinity) than 3%) MPa) UAMMetallurgical Fully None No thermal No HAZ No Very high ExceptionalExceptional Exceptional amorphous (~0%) stress (less (~0 Dilution(amorphous (40-80 (~0% than 50 inch) (~0%) alloy microinches)crystallinity MPa)/No 2,000-3,500 distortion MPa) (~0%)

UAM cladded part has: No thermal stress on substrate parts (no heataffected area) resulting in no distortion and no strain increasingproduct life; No fatigue reduction of the cladded parts; Superiorcorrosion resistance in severe environment (surface is fully amorphous);High Strength-to-Weight ratio; Superior surface characteristics andtribology performance.

Test Methodology

Amplitude of UAM: The amplitude is defined as peak-to-peak displacementof the horn at its work face. The unit is micrometer.

Load: load is measured using a load cell.

Foil thickness: thickness of the foils was measured using image analysistechnique of images obtained from light microscopy and SEM of mountedfoils. Other techniques for foil thickness measurement includemicrometer, caliper, stylus profilometry, interferometry, reflectometry,ellipsometry, spectrophotometry, ultrasound, advanced light focusedmicroscopy, ion beam analysis, tomography, and others.

Total cladding thickness: total cladding thickness was measured usingimage analysis technique of images obtained from light microscopy andSEM of mounted foils.

Speed of UAM cladding: The MTI sensor measured the displacement of thesonotrode parallel to its vibration direction.

Crystallinity: the degree of crystallinity is determined using X-raydiffraction technique and is defined as the ratio of intensity from thecrystalline peaks to the sum of the crystalline and amorphousintensities.

Porosity: porosity was measured using image analysis technique of imagesobtained from light microscopy and SEM of mounted samples

Thermal stress: thermal stress is calculated by multiplying the chanagein temperature, materials thermal expansion coefficient and material'sYoung's modulus.

Distortion: mechanical gages are used to measure the part distortion

Heat affected zone: optical microscopy and image analysis were used toobserve the heat affected zone of mounted and chemically etched areas.

Dilution: dilution is calculated from the proportion of base material inthe cladding material. X-ray fluorescence (XRF) has been used to measurethe elements concentration in base material and in the claddings.

Strength: strength is found by performing a tensile test.

Corrosion performance: ASTMB117 has been used for corrosion testing

Wear performance: ASTM G65 test has been used to analyze the wearperformance.

Surface finish as processed: surface finish was measured using aprofilometer and Ra has been reported.

Measurement of disjoint crystal: Transmission Electron Microscopy (TEM)and High-resolution SEM have been used to analyze the crystals.

PUBLICATIONS INCORPORATED BY REFERENCE

All publications and references, including patents and publications,cited herein the application are incorporated by reference in theirentirety.[1] S. Saunders, “NC State Researchers Successfully 3D Print MetallicGlass Alloys in Bulk,” 23 Mar. 2018. [Online]. Available:https://3dprint.com/207684/3d-print-metallic-glass-alloys/[2]S. Saunders, “Exmet AB's Amorphous Metals 3D Printing TechnologyReceives Investment Boost from AM Ventures, AcceleratingCommercialization,” 27 Mar. 2017. [Online]. Available:https://3dprint.com/169096/amorphous-metals-investment

[3] D. Hofman, P. Bordeenithikasem, S. Robers and A. Pate, “3D Printingof Bulk Metallic Glasses: Is it a Rebirth or the End of BMG Research,”in TMS 2019, 2019

[4] Y. Li, Y. Shen, M. Leu and H. Tsai, “Mechanical properties ofZr-based bulk metallic glass parts fabricated by laser-foil-printingadditive manufacturing,” Materials Science and Engineering A, pp.404-411, 2019.[5] D. Hofmann, P. Bordeenithikasem, Z. Dawson, L. Hamill, R. Dillon, B.McEnerney, S. Nutt and S. Bradford, “Investigating bulk metallic glassesas ball-and-cone locators for spacecraft deployable structures,”Aerospace Science and Technology, Vols. 82-83, pp. 513-519, November2018.[6] M. D. Demetriou, M. E. Launey, G. Garrett, J. P. Schramm, D. C.Hofmann, W. L. Johnson, R. O. Ritchie: A damage-tolerant glass, NatureMaterials 10 (2011) 123-128.[7] Oxford Instruments:http://www.ebsd.com/ebsd-explained/basics-of-automated-indexing.

What is claimed is:
 1. A cladded composite comprising a substrate and acladding layer comprising a bulk metallic glass on the substrate;wherein the bulk metallic glass comprises approximately 0-10%crystallinity, approximately 0% porosity, less than 50 MPa thermalstress, approximately 0% distortion, approximately 0 inch heat affectedzone, approximately 0% dilution, and a strength of about 2,000-3,500MPa.
 2. The cladded composite of claim 1, wherein the bulk metallicglass comprises Zr, Cu; wherein the substrate comprises steel, aluminumor titanium.
 3. The cladded composite of claim 2, wherein the bulkmetallic glass further comprises Ni, Al.
 4. The cladded composite ofclaim 3, wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm and the cladding layer has a thickness ofabout 0.02 mm to 5 mm.
 5. The cladded composite of claim 4, wherein thecladding layer comprises multiple sheets of the foil.
 6. The claddedcomposite of claim 1, wherein the bulk metallic glass comprises Zr, Ti;wherein the substrate comprises steel, aluminum or titanium.
 7. Thecladded composite of claim 6, wherein the cladding layer comprises afoil having a foil thickness of about 20-300 μm and the cladding layerhas a thickness of about 0.02 mm to 5 mm.
 8. The cladded composite ofclaim 7, wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm; wherein the cladding layer has a thicknessof about 0.1 mm to 0.4 mm.
 9. The cladded composite of claim 1, whereinthe cladded composite comprises a bond layer between the substrate andthe cladding layer.
 10. The cladded composite of claim 1, wherein thebulk metallic glass comprises Ni, C; wherein the substrate comprisessteel, aluminum or titanium.
 11. The cladded composite of claim 10,wherein the cladding layer comprises a foil having a foil thickness ofabout 20-300 μm and the cladding layer has a thickness of about 0.02 mmto 5 mm.
 12. The cladded composite of claim 11, wherein the bulkmetallic glass further comprises P or Si.
 13. The cladded composite ofclaim 1, wherein the bulk metallic glass comprises Fe, Co; wherein thesubstrate comprises steel, aluminum or titanium.
 14. The claddedcomposite of claim 13, wherein the bulk metallic glass further comprisesMo, B, Si, wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm and the cladding layer has a thickness ofabout 0.02 mm to 5 mm.
 15. The cladded composite of claim 1, wherein thebulk metallic glass comprises Ni, Si; wherein the substrate comprisessteel; wherein the cladding layer comprises a foil having a foilthickness of about 20-300 μm; wherein the cladding layer has a thicknessof about 0.02 mm to 5 mm.
 16. The cladded composite of claim 1, whereinthe bulk metallic glass comprises Co, Fe; wherein the substratecomprises steel; wherein the cladding layer comprises a foil having afoil thickness of about 20-300 μm; wherein the cladding layer has athickness of about 0.02 mm to 5 mm.
 17. The cladded composite of claim1, wherein the bulk metallic glass comprises Ti, Zr; wherein thesubstrate comprises aluminum; wherein the cladding layer comprises afoil having a foil thickness of about 20-300 μm; wherein the claddinglayer has a thickness of about 0.02 mm to 5 mm.
 18. The claddedcomposite of claim 1 further comprising an interlayer, wherein theinterlayer and the substrate has a disjoint crystal of less than <1micron in size.
 19. The cladded composite of claim 1, wherein the bulkmetallic glass comprises no crystallinity, no porosity, no thermalstress, no distortion, no heat affected zone and no dilution.
 20. Thecladded composite of claim 1, wherein the bulk metallic glass comprisesa first bulk metallic glass and the substrate comprises a second bulkmetallic glass.